US4424168A - Preparation of α-cyano-3-phenoxy-benzyl 3-alkenyl-2,2-dimethyl-cyclopropanecarboxylates - Google Patents
Preparation of α-cyano-3-phenoxy-benzyl 3-alkenyl-2,2-dimethyl-cyclopropanecarboxylates Download PDFInfo
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- US4424168A US4424168A US06/417,766 US41776682A US4424168A US 4424168 A US4424168 A US 4424168A US 41776682 A US41776682 A US 41776682A US 4424168 A US4424168 A US 4424168A
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- alkali metal
- process according
- hydrogen
- alkenyl
- fluorine
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- -1 α-cyano-3-phenoxy-benzyl Chemical group 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003085 diluting agent Substances 0.000 claims abstract description 14
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- MRLGCTNJRREZHZ-UHFFFAOYSA-N 3-phenoxybenzaldehyde Chemical compound O=CC1=CC=CC(OC=2C=CC=CC=2)=C1 MRLGCTNJRREZHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Chemical group 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 239000011737 fluorine Chemical group 0.000 claims description 12
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical group N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 7
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000005530 alkylenedioxy group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 125000002947 alkylene group Chemical group 0.000 abstract description 3
- 230000000361 pesticidal effect Effects 0.000 abstract description 2
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 238000002474 experimental method Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- 239000007858 starting material Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- CHLAOFANYRDCPD-UHFFFAOYSA-N 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carbonyl chloride Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(Cl)=O CHLAOFANYRDCPD-UHFFFAOYSA-N 0.000 description 5
- JDICMOLUAHZVDS-UHFFFAOYSA-N 4-fluoro-3-phenoxybenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1OC1=CC=CC=C1 JDICMOLUAHZVDS-UHFFFAOYSA-N 0.000 description 5
- 150000001733 carboxylic acid esters Chemical class 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 241001465754 Metazoa Species 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- FYIOXXUKFQPTJS-UHFFFAOYSA-N 2-(4-fluoro-3-phenoxyphenyl)-2-hydroxyacetonitrile Chemical compound N#CC(O)C1=CC=C(F)C(OC=2C=CC=CC=2)=C1 FYIOXXUKFQPTJS-UHFFFAOYSA-N 0.000 description 2
- IMPIIVKYTNMBCD-UHFFFAOYSA-N 2-phenoxybenzaldehyde Chemical class O=CC1=CC=CC=C1OC1=CC=CC=C1 IMPIIVKYTNMBCD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 150000003935 benzaldehydes Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 244000045947 parasite Species 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- DSTKWQCOVJAVCU-UHFFFAOYSA-N (4-fluoro-3-phenoxyphenyl)methyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=C(F)C(OC=2C=CC=CC=2)=C1 DSTKWQCOVJAVCU-UHFFFAOYSA-N 0.000 description 1
- BWPYAVCZZUTOBY-UHFFFAOYSA-N 2-(4-chlorophenyl)-3-methylbutanoyl chloride Chemical compound CC(C)C(C(Cl)=O)C1=CC=C(Cl)C=C1 BWPYAVCZZUTOBY-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- OLKWYZYVQYPFIM-UHFFFAOYSA-N 3-[2-chloro-2-(4-chlorophenyl)ethenyl]-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound OC(=O)C1C(C)(C)C1C=C(Cl)C1=CC=C(Cl)C=C1 OLKWYZYVQYPFIM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XOLBXXZZQLVKRU-UHFFFAOYSA-N C1CC1.[C] Chemical group C1CC1.[C] XOLBXXZZQLVKRU-UHFFFAOYSA-N 0.000 description 1
- GSINYWZNQFOYPT-UHFFFAOYSA-N CCOC(=O)CC.CCC(C)C(O)=O Chemical compound CCOC(=O)CC.CCC(C)C(O)=O GSINYWZNQFOYPT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- POGISOCYCQEQTF-UHFFFAOYSA-N [cyano(phenyl)methyl] cyclopropanecarboxylate Chemical class C1CC1C(=O)OC(C#N)C1=CC=CC=C1 POGISOCYCQEQTF-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- NQOUCSFLANJZBW-UHFFFAOYSA-N acetic acid;methyl formate Chemical compound COC=O.CC(O)=O NQOUCSFLANJZBW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HTRXGEPDTFSKLI-UHFFFAOYSA-N butanoic acid;ethyl acetate Chemical compound CCCC(O)=O.CCOC(C)=O HTRXGEPDTFSKLI-UHFFFAOYSA-N 0.000 description 1
- BRDOFYPYQFDHOQ-UHFFFAOYSA-N butyl acetate;hexanoic acid Chemical compound CCCCCC(O)=O.CCCCOC(C)=O BRDOFYPYQFDHOQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- QQODLKZGRKWIFG-UHFFFAOYSA-N cyfluthrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=C(F)C(OC=2C=CC=CC=2)=C1 QQODLKZGRKWIFG-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- HVHDXEBXZOWTMV-UHFFFAOYSA-N ethyl formate propanoic acid Chemical compound C(C)C(=O)O.C(=O)OCC HVHDXEBXZOWTMV-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- RCYSGAYIEFAJTG-UHFFFAOYSA-N methyl acetate;propanoic acid Chemical compound CCC(O)=O.COC(C)=O RCYSGAYIEFAJTG-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
Definitions
- the invention relates to an unobvious process for the preparation of certain known pesticidal ⁇ -cyano-3-phenoxybenzyl 3-alkenyl-2,2-dimethyl-cyclopropanecarboxylates.
- ⁇ -cyano-3-phenoxy-4-fluorobenzyl (cyclo-)-alkanecarboxylates such as ⁇ -cyano-3-phenoxy-4-fluoro-benzyl 3-(2,2-dichloro-vinyl)-2,2-dimethyl-cyclopropane-1-carboxylate or 3-(2-chloro-2-(4-chloro-phenyl)vinyl)-2,2-dimethyl-cyclopropanecarboxylate, or ⁇ -cyano-3-phenoxy-4-fluoro-benzyl ⁇ -isopropyl- ⁇ -(4-chloro-phenyl)acetate, are obtained when the corresponding acid-chlorides, such as 3-(2,2-dichloro-vinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid-chloride or 3-(2-chloro-2-(4-chlorophenyl))-vinyl-2,2-dimethyl-cyclo
- the yield and quality of the products are unsatisfactory in this preparation process.
- the cause of this may lie mainly in the fact that the ⁇ -cyano-3-phenoxy-4-fluoro-benzyl alcohol employed as the starting compound decomposes very readily into the starting components 3-phenoxy-4-fluoro-benzaldehyde and hydrogen cyanide, and is virtually impossible to prepare in pure form.
- substituted ⁇ -cyano-benzyl cyclopropanecarboxylates are obtained when substituted cyclopropanecarboxylic acid-halides are reacted with substituted benzaldehydes in the presence of aqueous solutions of sodium cyanide or potassium cyanide (see DE-OS (German Published Specification) No. 2,231,312/U.S. Pat. No. 3,835,176). According to this process, however, ⁇ -cyano-benzyl esters are also obtained only in moderate yields.
- DE-OS German Published Specification No. 2,708,590 discloses that ⁇ -phenyl-alkanecarboxylates can be obtained by the reaction of the corresponding acid-chlorides, alkali metal cyanide and benzaldehyde in a two-phase solvent system when special reaction conditions, such as a certain ratio of the amount of water to cyanide, are used.
- the ⁇ -cyano-phenoxybenzyl alkenylcyclopropanecarboxylates which are of particular interest as pesticides can be prepared in high yields in this manner, according to DE-OS (German Published Specification) No. 2,708,590, only when phase transfer catalysts are used for a short reaction time.
- the present invention now provides a process for the preparation of an ⁇ -cyano-3-phenoxy-benzyl 3-alkenyl-2,2-dimethyl-cyclopropanecarboxylate of the general formula ##STR4## in which R 1 and R 2 independently of each other represent a hydrogen or halogen atom,
- R 3 represents a hydrogen or halogen atom or an optionally substituted alkyl group
- R 4 represents a halogen atom, an optionally substituted alkyl or alkenyl group or an optionally substituted phenyl group or, together with R 3 , represents an alkanediyl (alkylene) radical,
- an alkali metal cyanide using an alkyl ester of a C 1 to C 6 carboxylic acid and water as diluents, if appropriate with the addition of an alkali metal bisulphite, at a temperature between -5° and +25° C.
- a particular advantage of the process according to the invention is that the formation of the various stereoisomers of compounds of the formula (I) can be controlled in such a manner that the proportion of the isomers of relatively high insecticidal action can be substantially increased in comparison with known processes-by the choice of the solvent alone or also by additives such as alkali metal bisulphites.
- Preferred 3-alkenyl-2,2-dimethyl-cyclopropanecarboxylic acid-chlorides of formula (II) to be used as starting materials are those in which
- R 3 represents a hydrogen, fluorine, chlorine or bromine atom or a methyl or trifluoromethyl group
- R 4 represents a fluorine, chlorine or bromine atom, a C 1 to C 5 alkyl, C 1 or C 2 fluoroalkyl or C 1 or C 2 chlorofluoroalkyl group, or a phenyl group which is optionally substituted by fluorine, chlorine or bromine and/or by one or more optionally fluorine-substituted or chlorine-substituted radicals selected from C 1 to C 4 alkyl, C 1 to C 4 alkoxy, C 1 to C 4 alkylthio and C 1 or C 2 alkylenedioxy, or the two radicals R 3 and R 4 together represent a C 2 to C 5 alkanediyl (alkylene) radical.
- Preferred 3-phenoxy-benzaldehydes of formula (III) further to be used as starting materials are those in which
- R 1 represents a hydrogen or fluorine atom
- R 2 preferably represents a hydrogen, fluorine, chlorine or bromine atom.
- Particularly preferred starting compounds of the formula (II) are those in which
- R 3 represents a fluorine, chlorine or bromine atom
- R 4 represents a fluorine, chlorine or bromine atom or a C 1 or C 2 fluoroalkyl, phenyl, 4-fluorophenyl or 4-chlorophenyl group.
- a particularly preferred starting compound of the formula (III) is that in which R 1 represents 4-fluoro and R 2 represents a hydrogen atom (i.e. 4-fluoro-3-phenoxybenzaldehyde).
- alkali metal cyanides which can be used in the process according to the invention are sodium cyanide and potassium cyanide.
- Alkyl esters of lower carboxylic acids which can be used as diluents in the process according to the invention are preferably methyl esters, ethyl esters, n- and isopropyl esters, and n-, iso- and sec-butyl esters of formic acid, acetic acid and propionic acid.
- formic acid methyl ester (methyl formate), formic acid ethyl ester (ethyl formate), acetic acid methyl ester (methyl acetate), acetic acid ethyl ester (ethyl acetate), propionic acid ethyl ester (ethyl propionate) and acetic acid n-butyl ester (butyl acetate).
- alkali metal bisulphites hydrogen sulphites or pyrosulphites
- sodium bisulphite is preferably employed as an additive.
- alkali metal bisulphites are employed in catalytic amounts.
- the reaction temperature is kept between -5° and +25° C., preferably between 0° and 15° C.
- the process is carried out under normal pressure.
- 1 to 200 parts by volume, preferably 20 to 120 or 1 to 3 parts by volume, of water are employed per 100 parts by volume of the alkyl ester of a C 1 to C 6 carboxylic acid.
- the starting compounds of the formulae (II) and (III) are dispersed in the carboxylic acid ester used as the diluent, and the aqueous cyanide solution is slowly metered in while stirring vigorously.
- the reaction mixture is stirred until the end of the reaction and is then diluted, if appropriate, with water and the carboxylic acid ester.
- the organic phase is separated off, washed with water, dried, and freed from the solvent in vacuo, the product of the formula (I) remaining as an oily residue.
- the starting compounds of the formula (III) and the alkali metal cyanide are dispersed in the carboxylic acid ester used as the diluent, which then preferably contains 1 to 3 parts of water, and the starting compound of the formula (II) is added dropwise.
- the reaction mixture is stirred until the end of the reaction; the alkali metal chloride formed as the coupling product is separated off by filtration (filtration under suction), and the solvent is distilled off from the filtrate under reduced pressure.
- the product, of the formula (I) which remains in the residue can be further purified by customary methods.
- the products of the formula (I) have 3 asymmetric carbon atoms and accordingly contain 8 optical isomers.
- An R configuration and an S configuration are possible in each case at the 3 asymmetric carbon atoms--the cyclopropane carbon atoms 1 and 3 and the benzyl carbon atom ⁇ .
- the present invention also provides a method of combating pests (especially insects) which comprises applying to the pests, or to a habitat thereof, a compound produced by the process of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
- the present invention also provides a method of freeing or protecting domesticated animals from parasites which comprises applying to said animals a compound produced by the process according to the present invention, in admixture with a diluent or carrier.
- the present invention further provides crops protected from damage by pests by being grown in areas in which immediately prior to and/or during the time of the growing a compound produced by the process of the present invention was applied alone or in admixture with a diluent or carrier.
- the present invention further provides domesticated animals whenever freed or protected from parasites by the application to said animals of a compound produced by the process according to the present invention, in admixture with a diluent or carrier.
- Reaction temperature 0° to 5° C. (prior art 20° to 25° C.).
- the effective stirring time was approximately 1 hour longer in each case (time for preparing and evaluating the chromatogram).
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813139314 DE3139314A1 (de) | 1981-10-02 | 1981-10-02 | Verfahren zur herstellung von 3-alkenyl-2,2-dimethyl-cyclopropancarbonsaeure-((alpha)-cyano-3-phenoxy-benzyl)-estern |
| DE3139314 | 1981-10-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4424168A true US4424168A (en) | 1984-01-03 |
Family
ID=6143291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/417,766 Expired - Fee Related US4424168A (en) | 1981-10-02 | 1982-09-13 | Preparation of α-cyano-3-phenoxy-benzyl 3-alkenyl-2,2-dimethyl-cyclopropanecarboxylates |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4424168A (da) |
| EP (1) | EP0076411A1 (da) |
| JP (1) | JPS5867659A (da) |
| BR (1) | BR8205784A (da) |
| DE (1) | DE3139314A1 (da) |
| DK (1) | DK438182A (da) |
| IL (1) | IL66889A0 (da) |
| ZA (1) | ZA827214B (da) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3835176A (en) | 1971-06-29 | 1974-09-10 | Sumitomo Chemical Co | Alpha-cyanobenzyl cyclopropanecarboxylates |
| US4110360A (en) | 1976-03-01 | 1978-08-29 | Shell Oil Company | Preparation of esters |
| US4123451A (en) | 1976-03-01 | 1978-10-31 | Shell Oil Company | Preparation of esters |
| US4280965A (en) | 1980-04-21 | 1981-07-28 | Ici Americas Inc. | Preparation of cyano substituted benzyl esters |
| DE2709264C3 (de) | 1977-03-03 | 1982-01-21 | Bayer Ag, 5090 Leverkusen | Substituierte Phenoxybenzyloxycarbonylderivate, Verfahren zu ihrer Herstellung und ihre Verwendung als Insektizide und Akarizide sowie neue Zwischenprodukte |
| US4350640A (en) | 1979-08-18 | 1982-09-21 | Bayer Aktiengesellschaft | Preparation of substituted (cyclo)alkanecarboxylic acid α-cyano-3-phenoxy-benzyl esters |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2844271A1 (de) * | 1978-10-11 | 1980-04-24 | Bayer Ag | 3-chlorostyryl-2,2-dimethyl-cyclopropancarbonsaeure-(4-fluoro-3-phenoxy- alpha -cyano-benzyl)-ester, verfahren zu ihrer herstellung und ihre verwendung als ektoparasitizide |
| DE2938112A1 (de) * | 1979-09-20 | 1981-04-16 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von (alpha) -cyano-phenoxy-benzyl-estern |
| DE3004092A1 (de) * | 1980-02-05 | 1981-08-13 | Bayer Ag, 5090 Leverkusen | Substituierte 3-(1,2-dibrom-alkyl)- 2,2-dimethyl-cyclopropan-1-carbonsaeureester, verfahren sowie zwischenprodukte zu ihrer herstellung und ihre verwendung in schaedlingsbekaempfungsmitteln |
-
1981
- 1981-10-02 DE DE19813139314 patent/DE3139314A1/de not_active Withdrawn
-
1982
- 1982-09-13 US US06/417,766 patent/US4424168A/en not_active Expired - Fee Related
- 1982-09-18 EP EP82108617A patent/EP0076411A1/de not_active Withdrawn
- 1982-09-28 JP JP57167752A patent/JPS5867659A/ja active Pending
- 1982-09-29 IL IL66889A patent/IL66889A0/xx unknown
- 1982-10-01 ZA ZA827214A patent/ZA827214B/xx unknown
- 1982-10-01 DK DK438182A patent/DK438182A/da not_active Application Discontinuation
- 1982-10-01 BR BR8205784A patent/BR8205784A/pt unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3835176A (en) | 1971-06-29 | 1974-09-10 | Sumitomo Chemical Co | Alpha-cyanobenzyl cyclopropanecarboxylates |
| US4110360A (en) | 1976-03-01 | 1978-08-29 | Shell Oil Company | Preparation of esters |
| US4123451A (en) | 1976-03-01 | 1978-10-31 | Shell Oil Company | Preparation of esters |
| DE2709264C3 (de) | 1977-03-03 | 1982-01-21 | Bayer Ag, 5090 Leverkusen | Substituierte Phenoxybenzyloxycarbonylderivate, Verfahren zu ihrer Herstellung und ihre Verwendung als Insektizide und Akarizide sowie neue Zwischenprodukte |
| US4350640A (en) | 1979-08-18 | 1982-09-21 | Bayer Aktiengesellschaft | Preparation of substituted (cyclo)alkanecarboxylic acid α-cyano-3-phenoxy-benzyl esters |
| US4280965A (en) | 1980-04-21 | 1981-07-28 | Ici Americas Inc. | Preparation of cyano substituted benzyl esters |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0076411A1 (de) | 1983-04-13 |
| IL66889A0 (en) | 1982-12-31 |
| DE3139314A1 (de) | 1983-04-21 |
| JPS5867659A (ja) | 1983-04-22 |
| ZA827214B (en) | 1983-08-31 |
| DK438182A (da) | 1983-04-03 |
| BR8205784A (pt) | 1983-09-06 |
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| AS | Assignment |
Owner name: BAYER AKTIENGESELLCHAFT; LEVERKUSEN, GERMANY A GE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:COLLN, REIMER;GALLENKAMP, BERND;DIEHR, HANS-JOACHIM;REEL/FRAME:004045/0454 Effective date: 19820903 Owner name: BAYER AKTIENGESELLCHAFT; A CORP., GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:COLLN, REIMER;GALLENKAMP, BERND;DIEHR, HANS-JOACHIM;REEL/FRAME:004045/0454 Effective date: 19820903 |
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